Sequential infiltration synthesis apparatus

ABSTRACT

Examples of the disclosure relate to a sequential infiltration synthesis apparatus comprising:a reaction chamber constructed and arranged to accommodate at least one substrate;a first precursor flow path to provide the first precursor to the reaction chamber when a first flow controller is activated;a second precursor flow path to provide a second precursor to the reaction chamber when a second flow controller is activated;a removal flow path to allow removal of gas from the reaction chamber;a removal flow controller to create a gas flow in the reaction chamber to the removal flow pathwhen the removal flow controller is activated; and,a sequence controller operably connected to the first, second and removal flow controllers and the sequence controller being programmed to enable infiltration of an infiltrateable material provided on the substrate in the reaction chamber. The apparatus may be provided with a heating system.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of, and claims priority to, U.S.Patent Application Ser. No. 15/380,909 filed Dec. 15, 2016 titledSEQUENTIAL INFILTRATION SYNTHESIS APPARATUS, the disclosure of which ishereby incorporated by reference in its entirety.

FIELD OF INVENTION

The present disclosure generally relates to apparatus and methods tomanufacture electronic devices. More particularly, the disclosurerelates to forming a structure on a substrate with an infiltrationapparatus.

BACKGROUND

As the trend has pushed semiconductor devices to smaller and smallersizes, different patterning techniques have arisen. These techniquesinclude spacer defined quadruple patterning, extreme ultravioletlithography (EUV), and EUV combined with Spacer Defined Doublepatterning. In addition, directed self-assembly (DSA) has beenconsidered as an option for future lithography applications. DSAinvolves the use of block copolymers to define patterns forself-assembly. The block copolymers used may include poly(methylmethacrylate) (PMMA), polystyrene, or poly(styrene-block-methylmethacrylate) (PS-b-PMMA). Other block copolymers may include emerging“high-Chi” polymers, which may potentially enable small dimensions.

The patterning techniques described above may utilize an infiltrateablematerial, such as an EUV polymer or DSA block copolymer resist, disposedon a substrate to enable high resolution patterning of the substrate. Tosatisfy the requirements of both high resolution and line-edgeroughness, the polymer resist may commonly be a thin layer. However,such thin polymer resists layer may have several drawbacks. Inparticular, high resolution polymer resists may have low etch resistanceand may suffer from high line edge roughness. This low etch resistanceand the high line edge roughness may makes the transfer of decentpatterned to underlying layers more difficult.

It may therefore be advantageous to infiltrate an infiltrateablematerial, for example the patterned material resist, to alter theproperties of the infiltrateable material. To perform infiltration ofthe patterned material it may be advantageously to have an optimizedinfiltration apparatus.

SUMMARY

In accordance with at least one embodiment of the invention there isprovided a sequential infiltration apparatus comprising:

-   -   a reaction chamber provided with a substrate holder to hold at        least one substrate;    -   a precursor distribution and removal system comprising one or        more reaction chamber valves to provide to and remove from the        reaction chamber a gaseous first and/or second precursor; and,    -   a sequence controller operably connected to the one or more        reaction chamber valves and being programmed to enable        sequential infiltration of an infiltrateable material provided        on the substrate in the reaction chamber with the gaseous first        and second precursor. The apparatus may be provided with a        heating system constructed and arranged to control the        temperature from the reaction chamber up to at least one of the        reaction chambers valves to avoid condensation. The heating        system may comprises heating elements to heat the reaction        chamber and at least one duct between the reaction chamber and        the reaction chamber valves to control the temperature from the        reaction chamber up to at least one of said chambers valves. The        temperature may be controlled to at least a boiling temperature        of the first or second precursor at the pressure of the first or        second precursor in the reaction chamber.

If a mixture of the first or second precursor with a mixing gas, such asfor example an inert gas, is used the pressure of the first or secondprecursor in the reaction chamber may be the partial pressure of saidprecursor. The partial pressure may be the desired maximum pressure thatmay be reached during infiltration of the first and/or second precursor.

The speed of the infiltration process may increase with the (partial)pressure of the precursors. Processing at higher pressure may thereforebe advantageously to maximize throughput but increases the risk ofcondensation on non-heated portions of the reaction chamber and any ductbetween the reaction chamber and the reaction chamber valves. Bycontrolling the temperature of the gaseous first or second precursor inthe reaction chamber up to the reaction chamber valves, the risk ofcondensation in the reaction chamber can be minimized.

The heating system may be constructed and arranged to control thetemperature of the reaction chamber and a duct from the reaction chamberto at least one of the reaction chamber valves to between 20 and 450°C., preferably between 50 and 150° C., more preferably between 60 and110 and most preferably between 65 and 95° C. The sequence controllermay be constructed and arranged to reach and/or maintain a (partial)pressure of the first or second precursor in the reaction chamberbetween 0.001 and 1000 Torr, preferably between 0.1 and 400 Torr, morepreferably between 1 and 100 Torr and most preferably between 2 and 50Torr during infiltration.

In accordance with a further embodiment there is provided a sequentialinfiltration apparatus comprising:

-   -   a reaction chamber provided with a substrate holder to hold at        least one substrate;    -   a precursor distribution and removal system comprising one or        more reaction chamber valves to provide to and remove from the        reaction chamber a gaseous first or second precursor; and,    -   a sequence controller operably connected to the one or more        reaction chamber valves and being programmed to enable        sequential infiltration of an infiltrateable material provided        on the substrate in the reaction chamber with the gaseous first        and second precursor. The apparatus may comprise a buffer tank        provided in the precursor distribution and removal system.

The buffer tank may be positioned upstream the reaction chamber to storefirst or second precursor. The buffer tank may have a volume between 0.1and 15, preferably between 0.3 and 3 and even more preferably between0.5 and 2 times the volume of the reaction chamber. The buffer tank maybe filled with the first or second precursor such that when the reactionchamber may be filled with said precursor it is more rapidly filledthereby increasing the throughput of the tool.

In accordance with yet a further embodiment there is provided asequential infiltration synthesis apparatus comprising:

-   -   a reaction chamber provided with a substrate holder to hold at        least one substrate;    -   a precursor distribution and removal system comprising one or        more reaction chamber valves to provide to and remove from the        reaction chamber a gaseous first or second precursor; and,    -   a sequence controller operably connected to the one or more        valves and being programmed to enable sequential infiltration of        a infiltrateable material provided on the substrate in the        reaction chamber with the gaseous first and second precursor,        wherein the apparatus comprises at least two reaction chambers        each chamber constructed and arranged to accommodate a single        substrate and the precursor distribution and removal system is a        partially common precursor distribution to provide to and remove        from the at least two reaction chambers the first or second        precursor simultaneously.

By having at least two reaction chambers the throughput of the apparatusmay be increased. By having a partially common first or second precursorflow path and a partially common removal flow path provided by theprecursor distribution and removal system the hardware in the apparatusmay be simplified and more efficiently used.

For purposes of summarizing the invention and the advantages achievedover the prior art, certain objects and advantages of the invention havebeen described herein above. Of course, it is to be understood that notnecessarily all such objects or advantages may be achieved in accordancewith any particular embodiment of the invention. Thus, for example,those skilled in the art will recognize that the invention may beembodied or carried out in a manner that achieves or optimizes oneadvantage or group of advantages as taught or suggested herein withoutnecessarily achieving other objects or advantages as may be taught orsuggested herein.

All of these embodiments are intended to be within the scope of theinvention herein disclosed. These and other embodiments will becomereadily apparent to those skilled in the art from the following detaileddescription of certain embodiments having reference to the attachedfigures, the invention not being limited to any particular embodiment(s)disclosed.

BRIEF DESCRIPTION OF THE FIGURES

It will be appreciated that elements in the figures are illustrated forsimplicity and clarity and have not necessarily been drawn to scale. Forexample, the dimensions of some of the elements in the figures may beexaggerated relative to other elements to help improve understanding ofillustrated embodiments of the present disclosure.

FIG. 1 depicts a sequential infiltration synthesis apparatus accordingto an embodiment.

FIG. 2 a and FIG. 2 b illustrate an infiltration method in accordancewith at least one embodiment of the invention for use in the sequentialinfiltration synthesis apparatus.

FIG. 3 depicts a reaction chamber of a sequential infiltration apparatusaccording to an embodiment.

FIG. 4 depicts a reaction chamber of a sequential infiltration apparatusaccording to a further embodiment.

FIG. 5 depicts a reaction chamber of a sequential infiltration apparatusaccording to an embodiment comprising a batch reactor.

FIG. 6 , FIG. 7 , FIG. 8 , FIG. 9 , FIG. 10 a , FIG. 10 b and FIG. 10 cdepict different configurations of sequential infiltration synthesisapparatus.

DETAILED DESCRIPTION

Although certain embodiments and examples are disclosed below, it willbe understood by those in the art that the invention extends beyond thespecifically disclosed embodiments and/or uses of the invention andobvious modifications and equivalents thereof. Thus, it is intended thatthe scope of the invention disclosed should not be limited by theparticular disclosed embodiments described below.

FIG. 1 depicts a sequential infiltration synthesis apparatus accordingto an embodiment. The apparatus comprises a reaction chamber 2 made of asuitable material such as steel, aluminum or quartz. A substrate 12provided with an infiltrateable material on top may be placed in thereaction chamber 2 on a substrate holder 10 by a substrate handler via asubstrate opening (not shown). The reaction chamber 2 forms a chamberclosed at one end by a flange, through which gases are introduced viaone or more openings provided with at least one (distribution) reactionchamber valve 19 to control opening and closing of said openings. Thedistribution reaction chamber valve 19 provides access of a fluiddistribution portion of the precursor distribution and removal system tothe reaction chamber 2.

The precursor distribution and removal system may provide a first or asecond precursor 28, 29 to the reaction chamber via the distributionreaction chamber valve 19. The first precursor 28 may be introduced as agas into the chamber 2 by evaporating a liquid or solid contained incontainer 30 by first precursor heater 32 to provide adequate vaporpressure for delivery into the chamber 2. The first precursor heater 32may provide heat to the first precursor in the container 30. Equally asecond precursor 29 may be introduced as a gas into the chamber 2 byevaporating a liquid or solid contained in container 31 by a secondprecursor heater 33 to provide adequate vapor pressure for delivery intothe reaction chamber 2.

A distribution buffer tank 18 may be provided in the gas distributionand removal system upstream of the reaction chamber valve 19 to storegas. The buffer tank may have a volume between 0.1 and 15, preferablybetween 0.3 and 3 and even more preferably between 0.5 and 2 times thevolume of the reaction chamber 2. The buffer tank may be filled with thefirst or second precursor such that when the reaction chamber should befilled with said precursor it is more rapidly filled thereby increasingthe throughput of the apparatus. The distribution buffer tank 18 may beheated.

As depicted the flow paths and the buffer tank for the first and secondprecursor may be partially common however they also may be separated.Separated flow paths with also separate buffer tanks make it possible toload both buffer tanks independently increasing throughput of theapparatus and provided efficient precursor usage. In case of separatedflow paths, each flow path may be provided with a separate distributionreaction chamber valve 19.

The precursor distribution and removal system may comprise a purgesystem to provide a purge gas 34 to the reaction chamber 2 via the purgevalve 24 and the distribution reaction chamber valve 19. As depicted theflow paths for purge gas, the first and second precursor may bepartially common however they also may be partially or completelyseparated. In case of separated flow paths, each flow path may beprovided with a separate distribution reaction chamber valve 19.

The purge gas may be an inert gas such as nitrogen and may be used topurge the reaction chamber 2. The purge gas may be used to purge thebuffer tank 18 as well.

Optionally, a separate exhaust (not depicted) between the buffer tank 18and the distribution reaction chamber valve 19 may be connected to thepump 39 to purge the buffer tank 18 more effectively while thedistribution reaction chamber valve 19 is closed.

Alternatively or additionally, the purge system may be constructed andarranged to provide the purge gas directly in to the reaction chamber 2via a purge reaction chamber valve (not shown) which directly providesthe purge gas in the reaction chamber 2. By providing the purge gasdirectly in the reaction chamber it becomes possible to use theprecursor distribution and removal system to load with precursor whilethe reaction chamber is purged. In this way it becomes possible toincrease throughput. The purge system may be provided with a purge gasbuffer chamber to urge more effectively.

The reaction chamber is closed at the other end by a flange whichconnects to a gas removal part of the precursor distribution and removalsystem via one or more openings provided with one or more reactionchamber valves 36, such as e.g., a gate valve. A gas removal pump 39and, optionally, a removal buffer tank 38 may be part of the gas removalportion of the precursor distribution and removal system.

The removal buffer tank 38 may be provided in the gas removal systemdownstream of the gate valve 36. The removal buffer tank 38 may have avolume between 1 and 30 and preferably between 5 and 15 times the volumeof the reaction chamber to suck gas in the removal buffer tank when thereaction chamber valve 36 is opened. The volume of the reaction chamber2 for substrates having a 300 mm diameter may be for a single substratereaction chamber 0.5-1 liter volume, for a single substrate reactionchamber with a showerhead above the substrate 3 to 5 liter and for abatch reactor chamber for 25 to 250 substrates 50-200 liter.

The reaction chamber 2 may be provided with an opening (not shown) toprovide substrates to the substrate holder 10. A door may be provided toclose and open the opening to provide access by a substrate handler tothe substrate holder 12. The substrate holder may also form part of thereaction chamber wall and may be moveable to provide access to thesubstrate holder 10.

The first precursor 28 may be a compound having an element of theinfiltration material to be formed in the infiltrateable material on thesubstrate 12. The first precursor 28 may be provided into the reactionchamber 2 through first precursor valve 20, buffer tank 18 anddistribution reaction chamber valve 19. FIG. 1 illustrates a system withtwo containers 30 and 31, each containing a first and second precursor28 and 29 respectively. However the type of infiltration material to beformed will determine the number of precursor and containers. Forexample, if a ternary infiltration material is desired, the apparatusmay include three containers and three precursor valves.

Also the containers 30 and 31 may be replaced with other suitableprecursor storage means if required. For example if one of theprecursors may be solid there may be provided specially adaptedcontainers to accelerate sublimation of the solid precursor. One of thecontainers 30, 31 may also be provided with a gaseous precursor suchthat heating is not required.

A sequence controller 40 e.g., a microcontroller may be operablyconnected to the one or more reaction chamber valves 19, 36, theprecursor valves 20, 22 and a purge valve 24. The sequence controller 40may comprise a memory M to store a program being programmed to enablethe apparatus to execute infiltration of the infiltrateable materialprovided on the substrate 12 in the reaction chamber 2 with the firstand second precursor 28, 29. A pressure and/or temperature sensor 26 maymonitor the chamber pressure and temperature and may be operablyconnected with the sequence controller 40 during operation to optimizethe process conditions of the infiltration. The program stored in thememory M of the sequence controller 40 may be programmed to sequence theopening and closing of the valves 19, 20, 22, 24 and 36 at theappropriate times to provide and remove the first and second precursorto the reaction chamber 2. The precursor valves 20, 22 may be heated.

The apparatus may be provided with a heating system comprising a firstheating element 14 e.g., a heating resistor wire and a heatingcontroller 16 operably connected to temperature sensors 26. One or moreof the temperature sensors 26 may be provided with a pressure sensor aswell. The heating controller 16 may be operably connected to thesequence controller 40. The temperature sensors 26 may be used tomeasure the temperature in the reaction chamber 2 and provide feedbackto the heating controller 16 about this temperature to adjust thetemperature of the heating element 14 to adjust the temperature of thereaction chamber 2.

The heating system 16 may control the temperature from the reactionchamber 2 up to at least one of the reaction chambers valves 19 or 36.The first heating element 14 may therefore be extending along thereaction chamber 2 up to said at least one reaction chamber valve 19 or36 to heat the reaction chamber 2. The first heating element 14 may heatthe reaction chamber 2 and at least one duct between the reactionchamber 2 and said at least one reaction chamber valve 19 or 36. Thefirst heating element may also heat one of the reaction chamber valves19, 36 to avoid condensation on said valve.

A precursor inflow duct between the (distribution) reaction chambervalve 19 and the reaction chamber 2 may be provided with a portion ofthe first heating element 14. This portion of the first heating element14 along the precursor inflow duct may be individually controlled withthe temperature sensor 26 extending in the inflow duct and the heatingcontroller 16 to adjust the temperature of the precursor inflow duct.

A precursor removal flow duct between the reaction chamber 2 and the(removal) reaction chamber valve 36 may be provided with a portion ofthe first heating element 14. This portion of the first heating element14 along the precursor removal flow duct may be individually controlledwith the temperature sensor 26 extending in the precursor removal flowduct and the heating controller 16.

In this way cold spots which may cause condensation in the reactionchamber 2, the precursor inflow duct and the precursor removal flow ductmay be avoided. Condensation of the precursor may cause that theprecursor is not effectively removable out of the reaction chamber intime and therefore the condensate may react with a subsequent precursorinto particles which may contaminate the reaction chamber and thesubstrate 12. Especially particles in the inflow duct deliveringprecursors may cause many problems.

The temperature may be set to an optimized process temperature. Thespeed of the infiltration process may increase with the pressure.Processing at higher pressure is therefore advantageously to maximizethroughput but increases the risk of condensation. The boilingtemperature of the first or second precursor at the maximum pressure ofthe first or second precursor in the reaction chamber 2 should be lowerthan the desired optimized process temperature to avoid condensation. Bycontrolling the temperature from the reaction chamber 2 up to at leastone of the reaction chamber valves 19, 36 the risk of condensation canbe minimized. It may also be advantageous to control the temperature inthe entire flow path from the containers 30 and 31 up to reactionchamber valve 36.

For example if the first or second precursor is trimethylaluminium (TMA)the vapor pressure is:

-   -   20° C.˜9 Torr    -   40° C.˜25Torr    -   60° C.˜64 Torr    -   80° C.˜149 Torr    -   100° C.˜313 Torr    -   128° C.˜760 Torr

As can be seen from these values the processing pressure can beincreased substantially by increasing the temperature in the reactionchamber. However if there is a small portion in the apparatus which isin contact with the precursor and which has a slightly lower temperaturethere is an immediate risk of condensation of the precursor which isunwanted.

The interaction of a precursor e.g., TMA with the infiltrateablematerial may be primarily through adsorption and diffusion. Thetemperature may have a significant effect on the infiltration becausethe rate of adsorption and diffusion and the equilibrium in anadsorption reaction may be impacted by changes in temperature.

The infiltration process may be optimal at 90° C. while at 120° C. and150° C. the infiltration is less good for TMA. This may be expected foran adsorption based process. At higher temperature the equilibrium ofthe adsorption reaction may shift towards separate TMA and polymerspecies. A process temperature between 20 and 400, preferably between 50and 150, more preferably between 60 and 110 and most preferably between65 and 95° C. is therefore preferred.

The heating system may therefore be constructed and arranged to controlthe temperature of the reaction chamber and a duct from the reactionchamber up to at least their respective reaction chamber valves tobetween 20 and 450, preferably between 50 and 150, more preferablybetween 60 and 110 and most preferably between 65 and 95° C. The memoryM in the sequence controller may be programmed with a program for theapparatus to reach and/or maintain a pressure of the first or secondprecursor in the reaction chamber between 0.001 and 1000 Torr,preferably between 0.1 and 400 Torr, more preferably between 1 and 100Torr and most preferably between 2 and 50 Torr during infiltration toavoid condensation. In this way we create a sufficient safety margin toavoid condensation in the apparatus while having an optimum processtemperature and pressure with respect to the use of the precursor TMA.

The apparatus may comprise a direct liquid injector (DLI) comprising aliquid flow controller and a vaporizer. The liquid flow controller maycontrol a liquid flow to an vaporizer to evaporate the first or secondprecursor. There may not be a need to heat the liquid flow between theflow controller and the vaporizer. The vaporizer may be heated toevaporate the first or second precursor. The heating system may beconstructed and arranged to control the temperature from the reactionchamber 2 up to the vaporizer to at least a boiling temperature of thefirst or second precursor at the pressure of the first or secondprecursor in the reaction chamber 2 to avoid condensation. The vaporizermay be constructed and arranged in the reaction chamber to directlyprovide the evaporated precursors in the reaction chamber. The vaporizermay also be constructed and arranged in the precursor distribution andremoval system of the apparatus.

The precursor distribution and removal system of the apparatus maycomprise at least one buffer tank 18, 38 provided in the precursordistribution and removal system. The buffer tank may be a distributionbuffer tank 18 positioned upstream of the reaction chamber 2 to storegaseous first or second precursor 28, 29 and has a volume between 0.1and 10 preferably between 0.3 and 3 and even more preferably between 0.5and 2 times the volume of the reaction chamber 2. The volume of thereaction chamber 2 for substrates having a 300 mm diameter may be for asingle substrate reaction chamber 0.5-1 liter volume, for a singlesubstrate reaction chamber with a showerhead above the substrate 3 to 5liter and for a batch reactor chamber for 25 to 250 substrates 50-200liter.

The distribution buffer tank 18 may be provided with a direct liquidinjector (DLI) vaporizer to directly inject the gaseous precursor in thebuffer tank. The distribution buffer tank 18 may comprise a flexiblebellow to accommodate different volumes in the buffer tank. Thedistribution buffer tank 18 may be provided in or near the top of thereaction chamber 2 to have a short delivery line to the reaction chamber2 and at the same time it may be heated by the reaction chamber.

The apparatus may comprise a second heating element 17 to control thetemperature of the precursor buffer tank 18 and/or the ducts in thefluid distribution part of the precursor distribution and removalsystem. The temperature of these parts may be controlled to 0 to 50,more preferably 0.1 to 20, even most preferably 0.2 to 10° C. above thetemperature of the reaction chamber 2. The second heating element 17 maybe controlled by the heating controller 16. A secondtemperature/pressure sensor (not depicted) may be provided to theprecursor buffer tank 18 and or the and/or the ducts in the fluiddistribution part and operably connected to the heating controller 16 toenhance control. By having the buffer tank 18 at a higher temperaturethan the reactor chamber 2 it becomes possible to maintain a highervapor pressure in the buffer tank 18 for the precursor so that a smallersize buffer tank is necessary to fill after opening distributionreaction chamber valve 19 the reactor chamber 2 in a short time span.

The first and second heating elements 14 and 17 may be a resistor wirebeing wound around the relevant portions of the apparatus. With a goodtemperature insulation and a relatively low working temperature around90° C. such an embodiment may work. The first and second heating element14, 17 may be multizone heating elements with multiple temperaturesensor to control the temperature in every part of the tool moreprecisely.

The precursor distribution and removal system may comprise a bubbler forproviding the precursor. The bubbler may provide a non-continuousprecursor flow having pulses of the first precursor of 0.1 to 200,preferably 1 to 3 seconds alternating with pulses of a mixing gas for0.01 to 2, preferably 0.3 to 1 seconds.

The precursor distribution and removal system may be provided with adirect liquid injector (DLI) vaporizer to directly inject the gaseousprecursor in the reaction chamber 2, in the distribution buffer tank 18or in other duct of the precursor distribution and removal systemupstream of the distribution reaction chamber valve 19.

The precursor distribution and removal system may have a removal buffertank 38 provided in the precursor distribution and removal systemdownstream of the reaction chamber after the removal reaction chambervalve 36 but before the removal pump 39. The removal buffer tank mayhave a volume between 1 and 20 and preferably between 5 and 15 times thevolume of the reaction chamber to suck gas in the buffer tank when theremoval reaction chamber valve 36 is opened.

Referring to FIG. 1 , during a typical operation, the first precursor 28is infiltrated in the infiltrateable material on the substrate byexposure to the first precursor 28 in vapor phase from the container 30.The first precursor 28 may react with the infiltrateable material on thesubstrate and become a chemi-sorbed or physi-sorbed derivativeinfiltrated in the infiltrateable material on the substrate.Subsequently the second precursor 29 is infiltrated in theinfiltrateable material on the substrate by exposure to the secondprecursor 29 in vapor phase from the container 31. The second precursor29 may react with the chemi-sorbed or physi-sorbed derivative of thefirst precursor 28 infiltrated in the infiltrateable material on thesubstrate to become the final infiltration material.

The containers 30, 31 for storing a first or second precursor beconstructed and arranged to store an alkyl compound of aluminum selectedfrom the group consisting of trimethyl aluminum (TMA), triethyl aluminum(TEA), and dimethylaluminumhydride (DMAH).

The containers 30, 31 may be constructed and arranged to store a firstor second precursor such as titanium(IV)chloride (TiCl),tantalum(V)chloride (TaCl5), and/or niobium chloride (NbCl5).

For infiltrating zirconium or hafnium the containers 30, 31 may beconstructed and arranged to store a Zr or Hf precursor. The Zr or Hfprecursor may comprise metalorganic, organometallic or halide precursor.In some embodiments the precursor is a halide. In some other embodimentsthe precursor is alkylamine compound of Hf or Zr, such as TEMAZ orTEMAH.

The containers 30, 31 may be constructed and arranged to store a firstor second precursor such as an oxidant chosen from the group comprisingwater, ozone, hydrogenperoxide, ammonia and hydrazine.

The apparatus may comprise a first container 31 for containing the firstor second precursor such as an aluminum or boron hydrocarbon compoundpreferably selected from the group consisting of trimethyl aluminum(TMA), triethyl aluminum (TEA), dimethylaluminumhydride (DMAH)dimethylethylaminealane (DMEAA), trimethylaminealane (TEAA),N-methylpyrroridinealane (MPA), tri-isobutylaluminum (TIBA),tritertbutylaluminum (TTBA) trimethylboron and triethylboron and asecond container 31 for containing the other of the first and secondprecursor such as a metal halide preferable from the group consisting oftitanium(IV)chloride (TiCl), tantalum(V)chloride (TaCl5), and niobiumchloride (NbCl5). The latter may be preferable for infiltrating metalcarbide material.

FIG. 2 a and b illustrate an infiltration method in accordance with atleast one embodiment of the invention for use in the apparatus of FIG. 1. The method includes a first step 50 of providing a substrate into areaction chamber with a substrate handler, the substrate having at leastone infiltrateable material on the substrate.

The infiltrateable material may be porous. Porosity may be measured bymeasuring the void spaces in the infiltrateable material as a fractionof the total volume of the infiltrateable material and may have a valuebetween 0 and 1. The infiltrateable material may be qualified as porousif the fraction of void spaces over the total volume is larger than 0.1,larger than 0.2 or even larger than 0.3.

The infiltrateable material may be an hardmask material, for example,comprise a spin on glass or spin on carbon layer, a silicon nitridelayer, an anti-reflective-coating or an amorphous carbon film. The spinon glass or spin on carbon layer may be provided by spinning a glass orcarbon layer on the substrate to provide the hardmask material. Further,the hardmask material may comprise SiCOH, or SiOC.

In an embodiment the infiltrateable material may be a patterned layerfor example a patterned (photo)resist layer. The resist layer may beannealed. The anneal step may have a purpose of degassing moisture orother contaminants from the resist, hardening the resist, selectivelyburning away portions of the resist from the substrate surface orcreating the required porosity.

In an embodiment the patterned layer may be provided by having a blockcopolymer film and promoting directed self-assembly of the blockcopolymer film to form the patterned layer. Infiltrating such patternedlayer may improve the quality of such patterned layer. The blockcopolymer film may, for example, have a low etch resistance and byinfiltrating the pattern in the copolymer the etch resistance of thepattern may be improved.

In an embodiment the patterned layer may be provided by having aphotoresist being exposed with a lithographic apparatus. Infiltratingsuch patterned layer may improve the quality of such patterned layer.The patterned photoresist layer may, for example, have a low etchresistance and by infiltrating the patterned photoresist the etchresistance of the pattern may be improved.

After the substrate is positioned in the reaction chamber 2 in FIG. 1during step 50 in FIG. 2 the reaction chamber and substrate may becleaned by the removal pump 39 evacuating the reaction chamber 2.Optionally a purge gas 34 may be provided with the purge system to flushthe reaction chamber 2 via the purge valve 24 and the distributionreaction chamber valve 19. The reaction chamber 2 may be heated toenhance outgassing.

The program in the memory M may be programmed to activate the precursordistribution and removal system to remove gas from the reaction chamber2 and to provide purge gas with the purge system to have the reactionchamber purged for 1 to 4000 seconds, preferably 100 to 2000 secondsbefore the infiltration is started. The program in the memory M may beprogrammed to activate the heater system 16 to heat the reaction chamber2 to a temperature between 20 and 450° C., preferably between 50 and150° C. and most preferably between 70 and 100° C. to enhance outgassingof contaminants.

Subsequently, the method comprises an infiltration method 51 in whichthe infiltrateable material may be infiltrated with the infiltrationmaterial during one or more infiltration cycles. Each infiltration cyclemay comprise the following steps:

Step 52 comprises providing a first precursor to the infiltrationmaterial on the substrate in the reaction chamber for a first period T1.The memory M of the sequence controller 40 may be provided with aprogram which when executed on the processor of the sequence controller40 makes the infiltration apparatus close the purging valve 24 and thedistribution reaction chamber valve 19 and builds up first precursor inthe duct of the precursor distribution and removal system upstream ofthe distribution reaction chamber valve 19 by opening the firstprecursor valve 20 and evaporating the first precursor 28 from the firstcontainer 30 by having the first precursor temperature controller 32activated to heat the container 32. The first precursor may be stored inthe buffer tank 18. The heating element 17 may be controlled by theheating controller 16 to heat the duct sufficiently to keep a high vaporconcentration in the duct and buffer tank 18 of the first precursor.

Then the program in the memory M of the sequence controller 40 may beprogramed to execute the opening of the valve 20 for a short period oftime to deliver the first precursor 28 to the reactor chamber 2. Thismay be done with the removal reaction chamber valve 36 opened and theremoval pump activated for a flush period FP to flush the reactionchamber 2 with the first precursor. The flush period FP may also beomitted. When the reaction chamber 2 is constructed and arranged toaccommodate a single substrate the program in the memory may beprogrammed to activate the first precursor flow controller for the flushperiod FP between 1 to 60, preferably between 2 and 30 seconds. When thereaction chamber is constructed and arranged to accommodate 2 to 25substrates the program in the memory may be programmed to have the flushperiod between 1 to 100, preferably between 2 and 50 seconds. When thereaction chamber is constructed and arranged to accommodate 26 to 200substrates and the program in the memory is programmed to have the flushperiod FP between 1 to 100, preferably between 5 and 50 seconds.

The first precursor may also be provided to the reactor chamber 2 withthe precursor distribution and removal system while not removing anyprecursor with the removal pump 39 for a load period LP by closing theremoval reaction chamber valve 36 by the program installed in a memory Mof the sequence controller 40. This results in a pressure buildup of thefirst precursor in the reaction chamber 2. This build up may beterminated by the sequence controller 40 when the pressure of the firstor second precursor in the reaction chamber 2 reaches a maximum desiredinfiltration pressure. Alternatively, there may be a pressure releasevalve which opens when the pressure in the reaction chamber increasesabove a predetermined maximum which may also end the pressure loadperiod LP.

Subsequently the first precursor may be maintained residing stationaryin the reaction chamber 2 while having the precursor distribution andremoval system not providing or removing any precursor for a soak periodSP. This may be done by the sequence controller 40 closing the reactorchamber valves 19 and 36 in accordance with the program stored in thememory M. When the reaction chamber 12 is constructed and arranged toaccommodate a single substrate the program in the memory M may beprogrammed to activate the first precursor flow controller for the loadperiod LP between 1 to 3000, preferably between 3 and 1000, morepreferably between 5 to 500 seconds; and the soak period SP between 10to 9000, preferably between 50 and 5000 seconds and more preferablybetween 100 and 1000 seconds. When the reaction chamber 12 isconstructed and arranged to accommodate 2 to 25 substrates the programin the memory sequence controller may be programmed with the load periodLP between 1 to 3000, preferably between 3 and 1000, more preferablybetween 5 to 500 seconds; and the soak period SP between 10 to 12000,preferably between 15 and 6000 seconds and more preferably between 20and 1000 seconds. When the reaction chamber 12 is constructed andarranged to accommodate 26 to 200 substrates the program in the memory Mmay be programmed to have the load period LP between 1 to 3000,preferably between 3 and 1000, more preferably 5 to 500 seconds; and thesoak period SP between 10 to 14000, preferably between 50 and 9000seconds, more preferably between 100 and 5000 and most preferablybetween 100 and 800 seconds.

The first period T1 therefore may comprise a flush period FP, a loadperiod LP, and/or a soak period SP. During the whole period T1 the firstprecursor may infiltrate and absorb in the infiltrateable material.

The memory M of the sequence controller 40 may be programmed with theprogram when executed on a processor of the sequence controller makingthe infiltration apparatus to provide the first precursor for the firstperiod T1 between 1 to 20000, preferably between 20 to 6000, morepreferably between 50 and 4000, and most preferably between 100 and 2000seconds in step 52. In this way a deep infiltration of the firstprecursor in the infiltrateable material may be assured.

In step 53 a portion of the first precursor is removed for a secondperiod T2. The sequence controller 40 may open the removal reactionchamber valve 36 to remove first precursor with the vacuum pump 38 fromthe reaction chamber 2. Additionally a purge gas 34 may be provided withthe purge system to flush the reaction chamber 2 by opening the purgevalve 24 and the distribution reaction chamber valve 19 with thesequence controller 40. The buffer tank 18 may be used to provide thepurge gas more rapidly in the reaction chamber 2 by storing purge gas inthe buffer tank.

The program in the memory M of the sequence flow controller 40 may beprogrammed with a program when executed on a processor of the sequencecontroller 40 will make the infiltration apparatus to control the secondduration T2 of removing the portion of the first precursor. The programin the memory M may be programmed with the second period T2 between 1 to20000, preferably between 20 to 6000, more preferably between 50 and4000, and most preferably between 100 and 2000 seconds.

In step 54 the second precursor is provided in the reaction chamber 2 bythe sequence controller 40 activating the precursor distribution andremoval system to provide and maintain the second precursor for a thirdduration T3 in the reaction chamber. The memory M of the sequencecontroller 40 may be programmed to close the purging valve 24 and thedistribution reaction chamber valve 19 and building up second precursorin the duct of the precursor distribution and removal system upstream ofthe distribution reaction chamber valve 19 by opening the secondprecursor valve 22 and evaporating the second precursor 29 from thesecond container 31 by having the second precursor temperaturecontroller 33 activated to heat the second container 31. The secondprecursor may be stored in the buffer tank 28. The heating element 17may be controlled by the heating controller 16 to heat the ductsufficiently to keep a high vapor concentration in the duct and buffertank 18. Then the memory M of the sequence controller 40 may beprogramed to open valve 20 for a short period of time to deliver thesecond precursor 28 to the reactor chamber 2.

The flush period FP, load period LP, and soak period SP have beendescribed in conjunction with the first precursor. The memory M of thesequence controller may be provided with a program when executed on theprocessor of the sequence controller 40 will make the infiltrationapparatus run the third period 54 with a flush period FP, a load periodLP, and/or a soak period SP of the second precursor as explained in FIG.2 b . During the whole third period T3 the second precursor mayinfiltrate the infiltrateable material and react with the absorbed firstprecursor derivative in the infiltrateable material. Resulting in areaction with the absorbed first precursor derivative resultingreinforcement of the infiltrateable material with infiltrated material.

Optionally the infiltration cycle may have a step 55 in which a portionof the second precursor may be removed for a fourth period T4. Thesequence controller 40 may open the removal reaction chamber valve 36 toremove first precursor with the vacuum pump 38 from the reaction chamber2. Additionally a purge gas 34 may be provided with the purge system toflush the reaction chamber 2 by opening the purge valve 24 and thedistribution reaction chamber valve 19 with the sequence controller 40.

The memory M of the sequence controller may be programed so that whenthe program is executed on a processor of the sequence controller 40 ofan infiltration apparatus the infiltration sequence may be repeated Ntimes, wherein N is between 1 to 20, preferably 3 to 15 and mostpreferably between 6 to 12. The precursors 28 and 29 may be chosen suchthat the precursors form a metal or dielectric infiltration material inthe infiltrateable material.

The first precursor and the second precursor may be utilized together inthe apparatus of FIG. 1 to infiltrate the infiltrateable materialaccording to the program of FIGS. 2 a and 2 b with aluminum oxide(Al2O3), silicon oxide, (SiO2), silicon nitride (SiN), siliconoxynitride (SiON), silicon carbonitride (SiCN), silicon carbide (SiC),titanium carbide (TiC), aluminum nitride (AlN), titanium nitride (TiN),tantalum nitride (TaN), tungsten (W), cobalt (Co), titanium oxide(TiO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), or hafnium oxide(HfO2).

Optionally, the infiltration material such as a metal or dielectric maybe deposed on top of the whole volume of the infiltrateable materialwith the infiltration apparatus as well. This may, for example, be doneif the infiltrateable material is patterned to make the pattern widerand more etch resistant.

FIG. 3 depicts a sequential infiltration apparatus according to afurther embodiment. The reaction chamber 2 is provided with a substrate12 on a substrate holder 10. The precursor distribution and removalsystem provides the first or second precursors from one side of thereaction chamber 2 via entry port 66 to the substrate 12. The entry port66 may be provided with a buffer tank 18 and closeable with a valve 19.An exit port 67 is provided to the distribution and removal system toremove the precursor from the reaction chamber 2 on the other side. Inthis configuration the reaction chamber 2 will be a cross flow reactionchamber in which precursors latterly flow over the substrate.

The substrate holder 10 for holding the substrate 12 may be moveable upand down. The substrate holder 10 may be moveable underneath an edge 68of the top portion of the reaction chamber 2 to allow a substratehandler (not depicted) to provide or remove a substrate from thesubstrate holder 10. By moving it up the reaction chamber can be closedagain. The substrate holder 10 may comprise a third heating element forheating of the substrate 12.

An advantage of the embodiment according to FIG. 3 is that the reactionchamber 2 may have a small volume of 0.5-1 liter for a single substratereaction chamber 2. The small volume making it possible to have a lowprecursor usage. The space between substrate and the top of the reactionchamber may therefore be less than 1 centimeter, preferably less than 5mm and most preferably less than 3 mm.

FIG. 4 depicts a sequential infiltration apparatus according to afurther embodiment. The reaction chamber 2 comprises a showerhead 69.The showerhead 69 may be provided in the top portion of the reactionchamber 2. The showerhead 61 may be connected with the precursordistribution and removal system to provide the first or secondprecursors 28, 29 to the surface of the substrate 12 directly. Theprecursor distribution and removal system may remove the first or secondprecursors 28, 29 by the opening 67. The purge system may also beconnected to the showerhead 69 to purge the reaction chamber 2.

The showerhead 69 may also be connected with the precursor distributionand removal system to remove the first or second precursors from thereaction chamber 2. The opening 67 may be connected to the purge systemto purge the reaction chamber 2 in such case.

The substrate holder 10 for holding the substrate 12 may be moveable upand down. The substrate holder 10 may comprise a third heating elementfor heating of the substrate 12. An advantage of this embodiment is thatthe showerhead rapidly provides and removes precursor from the surfaceof the substrate while the volume still is acceptable between 2 to 5liter, preferably 3 to 4 liter.

FIGS. 5, 6, 7, 8 and 10 a-10 c show different configurations ofsequential infiltration synthesis apparatus. The sequential infiltrationsynthesis apparatus according to FIGS. 5, 6, 7, 8 and 10 may use thesame precursor distribution and removal system as explained inconjunction with FIGS. 1 and 2 .

FIG. 5 depicts a sequential infiltration apparatus according to afurther embodiment. The apparatus comprises a batch reactor chamber 70for 25 to 250 substrates with a volume of 50-200 liter. The substratesmay be loaded in a boat 71 which is provided with substrate holders toaccommodate the 25 to 250 substrates with a substrate handler. The boat71 with the substrates may be moved in the reaction chamber 70 in oncefrom underneath. The bottom part 71A of the boat 70 may seal thereaction chamber 70. A heating element 40 may be provided to control thetemperature of the reaction chamber 70. First and second precursor maybe provided with the inlet 72 and may be removed via outlet 73 of theprecursor distribution and removal system. Valves may be used to controlthe gas flow and care should be taken to ensure that the evaporatedprecursors are kept at a temperature above their boiling temperature inthe reaction chamber 70. This may be done by having the heating elementto control the temperature in the inlet 72 and the outlet 73 as well upto the valves (e.g., reaction chamber valve 36).

In case the apparatus is provided with a direct liquid injector (DLI)comprising a liquid flow controller and a vaporizer, the liquid flowcontroller may control a liquid flow to the vaporizer which evaporatesthe first or second precursor. There may not be a need to heat theliquid flow between the flow controller and the vaporizer. The vaporizermay be heated to evaporate the first or second precursor directly.

The vaporizer may be provided in the batch reactor chamber to directlyprovide the first or second precursor in the chamber. A batch reactormakes it possible to infiltrate a large number of substrates at the sametime improving the throughput of the apparatus.

FIGS. 6, 7, 8 and 10 a-10 c show different configurations of sequentialinfiltration synthesis apparatus. The sequential infiltration synthesisapparatus according to FIGS. 6, 7, and 8 may use the reaction chamber 2as described in conjunction with FIG. 3 or 4 .

Shown are cassette loading stations 74 for loading cassettes (e.g.,Front Opening Unified Pod's FOUP) with multiple substrates. A firstsubstrate handler 75 is used to move the substrates from the cassettesto an intermediate loading station 76. Subsequently, a second substratehandler 77 is used to move the substrates from the intermediate loadingstation 76 to a processing station provided with the substrate holder10. In FIG. 6 a single substrate holder 12 is accessible by the secondsubstrate holder 77 for a single substrate which can be processed in thereaction chamber 2. In the embodiment of FIG. 6 four substrates can beprocessed simultaneously.

A partially common precursor distribution and removal system to provideto and remove from at least two reaction chambers the first or secondprecursor is provided. The partially common precursor distribution andremoval system may share the reaction chamber valves. The reactionchamber valves may also be separate for each reaction chamber. Thecommon part of the precursor distribution and removal system may befurther provided downstream of the (distribution) reaction chamber valve19 and downstream of the (removal) reaction chamber valve 36 asexplained in conjunction with FIG. 1 . In this way economical use of theprecursor distribution and removal system can be made.

Heating elements may be provided to heat the reaction chamber 2, thesubstrate holder 10 and/or a duct in the precursor distribution andremoval system up to any of the reaction chamber valves. At least onebuffer tank may be provided in the precursor distribution and removalsystem.

In the embodiment of FIGS. 7 and 8 the processing stations are providedwith multiple substrate holders 10 and are provided with a moveable(e.g., rotatable) body 78 (alternatively a rotating substrate supportframe may be used) and by rotating this body 78 (or the support frame)all the substrate holders 10 can be provided with substrates by thesecond substrate handler 77. The substrate holders 10 can be movedupwards to close and form a reaction chamber 2. Alternatively oradditionally a door 80 may be provided to close the space with thereaction chamber(s).

In the embodiment of FIG. 7 it may be eight substrate holders that formeight reaction chambers processing a single substrate or it may be eightsubstrate holders that form two shared reaction chambers each sharedreaction chamber processing four substrates.

In the embodiment of FIG. 7 it may be possible to dedicate thesubstrates (normally 25) in a particular FOUP on the cassette loadingstation 74 to a particular body 78 so that all the substrates in a FOUPare processed on the same body 78 and the reaction chamber (relatingthereto). The advantage being that if there is an error found in theprocessing of one FOUP it is known in which part of the infiltrationapparatus it occurred. In the embodiment of FIG. 7 two times foursubstrates can be processed simultaneously.

In the embodiment of FIG. 8 the first and second substrate handler 75,77 may be provided with a dual substrate support to handle twosubstrates at the same time to increase throughput. The moveable boy 78can be rotated around axis 82 to provide access of the second substratehandler 78 to the different substrate holders 10. In the embodiment ofFIG. 8 it may be sixteen substrate holders 10 that form sixteen reactionchambers processing a single substrate or it may be sixteen substrateholders 10 that form four shared reaction chambers each shared reactionchamber processing four substrates. In the embodiment of FIG. 8 fourtimes four substrates can be processed simultaneously giving theapparatus a high productivity.

FIG. 9 discloses a cross section of a processing station of theembodiments of FIGS. 7 and 8 . A moveable body 78 is provided forholding two or more (e.g., 3, 4, 5, or 6) substrates 12. The moveablebody 78 can be moved upwards against the sealing 81 to close and createtwo or more reaction chambers 2. The moveable body 78 can be rotatedaround axis 82 to provide access of the second substrate handler 78 todifferent substrates 12 on the substrate holder 10.

A partially common precursor distribution and removal system to provideto and remove from the at least two reaction chambers 2 the first orsecond precursor is provided. The partially common precursordistribution and removal system shares the reaction chamber valves 19and 36. The common part of the precursor distribution and removal systemis further provided upstream of the (distribution) reaction chambervalve 19 and downstream of the (removal) reaction chamber valve 36 asexplained in conjunction with FIG. 1 . In this way economical use of theprecursor distribution and removal system can be made.

Heating elements may be provided to heat the reaction chamber 2, thesubstrate holder 10 and/or a duct in the precursor distribution andremoval system up to any of the reaction chamber valves 19, 36. At leastone buffer tank may be provided in the precursor distribution andremoval system.

In an embodiment not shown five processing stations with each fivesubstrate holders may be provided to process simultaneously a completeFOUP with 25 substrates guaranteeing short processing times for acomplete FOUP.

FIGS. 10 a 10 b and 10 c depict a further embodiment according to theinvention. In this embodiment a processing station 90 is provided withslits 91 which can function as a substrate holder 10 (see FIG. 10 cwhich shows a cross section through the slit 91). Cassette loadingstations 74 are provided for loading cassettes (e.g., Front OpeningUnified Pod's FOUP) with multiple substrates. A first substrate handler(not shown but similar to first substrate handlers 75 in FIGS. 6 and 7 )may be used to move the substrates from the cassettes to an intermediateloading station (not shown but similar to intermediate loading station76 in FIGS. 6 and 7 ). A second substrate handler (not shown but similarto second substrate handlers 77 in FIGS. 6 and 7 ) may providesubstrates to the slits 91 from the intermediate loading station. A doormay close the slits 91 to create a reaction chamber and the substratesmay be processed at the processing station 90.

A partially common precursor distribution and removal system 93 may beprovided to provide and remove from all the substrates in the slits 91the first or second precursor simultaneously. Five substrates may beprocessed simultaneously in processing station 90 which has theadvantage that a complete FOUP with 25 substrates at the cassettestation 74 can be processed in five processing stations 90. Since theapparatus has eight processing station 90 it may be possible to processforty substrates simultaneously guaranteeing short processing times fora complete FOUP.

First heating elements may be provided to heat the reaction chamber inthe slits 91 in the processing station 90 and/or a duct in the precursordistribution and removal system 93. Advantageously this may be done upto any of the reaction chamber valves in the precursor distribution andremoval system 93. At least one buffer tank may be provided in theprecursor distribution and removal system 93.

The particular implementations shown and described are illustrative ofthe invention and its best mode and are not intended to otherwise limitthe scope of the aspects and implementations in any way. Indeed, for thesake of brevity, conventional manufacturing, connection, preparation,and other functional aspects of the system may not be described indetail. Furthermore, the connecting lines shown in the various figuresare intended to represent exemplary functional relationships and/orphysical couplings between the various elements. Many alternative oradditional functional relationship or physical connections may bepresent in the practical system, and/or may be absent in someembodiments.

It is to be understood that the configurations and/or approachesdescribed herein are exemplary in nature, and that these specificembodiments or examples are not to be considered in a limiting sense,because numerous variations are possible. The specific routines ormethods described herein may represent one or more of any number ofprocessing strategies. Thus, the various acts illustrated may beperformed in the sequence illustrated, in other sequences, or omitted insome cases.

The subject matter of the present disclosure includes all novel andnonobvious combinations and sub-combinations of the various processes,apparatus, systems, and configurations, and other features, functions,acts, and/or properties disclosed herein, as well as any and allequivalents thereof.

What is claimed is:
 1. A sequential infiltration synthesis apparatuscomprising: a reaction chamber provided with a substrate holder to holdat least one substrate; a precursor distribution and removal systemcomprising: one or more upstream and downstream reaction chamber valvesto provide to and remove from the reaction chamber a gaseous firstprecursor and/or a gaseous second precursor; and, a sequence controlleroperably connected to the one or more upstream and downstream reactionchamber valves and being programmed to enable sequential infiltration ofan infiltrateable material provided on the substrate in the reactionchamber with the gaseous first precursor and the gaseous secondprecursor, wherein the sequential infiltration synthesis apparatus isprovided with a first heating system constructed and arranged to controlthe temperature of the reaction chamber, wherein the sequence controllerprovides the first precursor to the reaction chamber with the precursordistribution and removal system while not removing any precursor for aload period LP, resulting in a pressure buildup in the reaction chamber,and terminating the load period LP when the pressure of the gaseousfirst precursor or the gaseous second precursor in the reaction chamberreaches a desired infiltration pressure.
 2. The sequential infiltrationsynthesis apparatus according to claim 1, wherein the precursordistribution and removal system further comprises a buffer tank upstreamof reaction chamber.
 3. The sequential infiltration synthesis apparatusaccording to claim 2, further comprising a second heating systemconstructed and arranged to control the temperature of the gaseous firstand/or second precursors stored in the distribution buffer tank to a pretemperature 0 to 50° C. above the temperature of the reaction chamber.4. The sequential infiltration synthesis apparatus according to claim 1,wherein the precursor distribution and removal system further comprisesa removal buffer tank downstream of the reaction chamber.
 5. Thesequential infiltration synthesis apparatus according to claim 4,wherein the removal buffer tank has a volume that is 1 to 30 timesgreater than a volume of the reaction chamber.
 6. The sequentialinfiltration synthesis apparatus according to claim 1, wherein theinfiltrateable material is porous.
 7. The sequential infiltrationsynthesis apparatus according to claim 1, wherein at least one of theone or more of the upstream and downstream reaction chamber valvescomprises a liquid flow controller in a liquid injection system.
 8. Thesequential infiltration synthesis apparatus according to claim 1,wherein the precursor distribution and removal system comprises a ductbetween the reaction chamber and at least one of the one or more of theupstream and downstream reaction chamber valves to provide or remove agaseous precursor.
 9. The sequential infiltration synthesis apparatusaccording to claim 1, wherein the sequence controller is programmed to:leave the gaseous first precursor or the gaseous second precursor in thereaction chamber while having the precursor distribution and removalsystem deactivated for a soak period SP after terminating the loadperiod LP.
 10. The sequential infiltration synthesis apparatus accordingto claim 1, wherein the sequence controller is programmed to: providethe gaseous first precursor to the reactor chamber with the precursordistribution and removal system while removing any precursor for a flushperiod FP before and/or after the load period LP.
 11. The sequentialinfiltration synthesis apparatus according to claim 1, whereinterminating the load period LP comprises closing an upstream reactionchamber valve and opening a downstream reaction chamber valve of the oneor more upstream and downstream reaction chamber valves.
 12. Asequential infiltration synthesis apparatus comprising: a reactionchamber provided with a substrate holder to hold at least one substrateand a first heating system constructed and arranged to control thetemperature of the reaction chamber to a process temperature; aprecursor distribution and removal system comprising one or moreupstream and downstream reaction chamber valves to provide to and removefrom the reaction chamber a gaseous first precursor or a gaseous secondprecursor; and, a sequence controller operably connected to the one ormore of the one or more of the upstream and downstream reaction chambervalves and being programmed to enable sequential infiltration of aninfiltrateable material provided on the substrate in the reactionchamber with the gaseous first precursor and the gaseous secondprecursor, wherein the sequence controller provides the gaseous firstprecursor to the reaction chamber with the precursor distribution andremoval system while not removing any precursor for a load period LP,resulting in a pressure buildup in the reaction chamber, and terminatingthe load period LP when the pressure of the gaseous first precursor orthe gaseous second precursor in the reaction chamber reaches a desiredinfiltration pressure, wherein the one or more of the one or more of theupstream and downstream reaction chamber valves comprises a distributionreaction chamber valve that is upstream of the reaction chamber.
 13. Thesequential infiltration synthesis apparatus according to claim 12,wherein the precursor distribution and removal system comprises at leastone distribution buffer tank.
 14. The sequential infiltration synthesisapparatus according to claim 13, wherein the distribution buffer tank isprovided with a second heating system.
 15. The sequential infiltrationsynthesis apparatus according to claim 14, wherein the gaseous firstprecursor and the gaseous second precursor are both configured to flowthrough the distribution buffer tank and through the distributionreaction chamber valve.
 16. The sequential infiltration synthesisapparatus according to claim 12, wherein the precursor distribution andremoval system comprises a removal buffer tank disposed between adownstream reaction chamber valve and a gas removal pump.
 17. Thesequential infiltration synthesis apparatus according to claim 16,wherein a volume of the removal buffer tank is greater than a volume ofthe reaction chamber.
 18. A sequential infiltration synthesis apparatuscomprising: a reaction chamber provided with a substrate holder to holdat least two substrates; a precursor distribution and removal systemcomprising one or more upstream and downstream reaction chamber valvesto provide to and remove from the reaction chamber a gaseous firstprecursor and a gaseous second precursor; and, a sequence controlleroperably connected to the one or more upstream and downstream reactionchamber valves and being programmed to enable sequential infiltration ofan infiltrateable material provided on the two substrates in thereaction chamber with the gaseous first precursor and the gaseous secondprecursor, wherein the sequence controller provides the first precursorto the reaction chamber with the precursor distribution and removalsystem while not removing any precursor for a load period LP, resultingin a pressure buildup in the reaction chamber, and terminating the loadperiod LP when the pressure of the gaseous first precursor or thegaseous second precursor in the reaction chamber reaches a desiredinfiltration pressure.
 19. The sequential infiltration synthesisapparatus according to claim 18, wherein the reaction chamber comprisesat least two reaction spaces, each reaction space constructed andarranged to accommodate a single substrate.
 20. The sequentialinfiltration synthesis apparatus according to claim 19, wherein the tworeaction spaces are connected to a common upstream reaction chambervalve of the precursor distribution and removal system to provide to theat least two reaction spaces the gaseous first precursor or the gaseoussecond precursor.